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Activation energy and nonequilibrium effects in thermal reactions
Author(s) -
Penner Alvin P.,
Bhattacharjee Rakhal C.,
Forst Wendell
Publication year - 1977
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550090306
Subject(s) - chemistry , arrhenius equation , non equilibrium thermodynamics , activation energy , atmospheric temperature range , thermodynamics , vibrational energy , range (aeronautics) , negative temperature , reaction rate constant , thermal , atomic physics , kinetics , physics , molecule , classical mechanics , organic chemistry , materials science , composite material
Abstract Calculations of the nonequilibrium rate constant for the model system H 2 O 2 + M → 2 OH + M over the temperature range of 300–1900°K, assuming that only vibrational, or that both vibrational and rotational, energy is transferred in a collision, show that (1) inefficient energy transfer leads to a distinctly non‐Arrhenius temperature dependence, the nonlinearity being in principle different for different M, and (2) despite different activation energies for different M, the order of M efficiencies is preserved throughout the temperature range. A reversal of M efficiencies can occur only if there is a change of mechanism of the reaction over the temperature range investigated.